JP5287281B2 - Pneumatic tire manufacturing method and pneumatic tire - Google Patents
Pneumatic tire manufacturing method and pneumatic tire Download PDFInfo
- Publication number
- JP5287281B2 JP5287281B2 JP2009008779A JP2009008779A JP5287281B2 JP 5287281 B2 JP5287281 B2 JP 5287281B2 JP 2009008779 A JP2009008779 A JP 2009008779A JP 2009008779 A JP2009008779 A JP 2009008779A JP 5287281 B2 JP5287281 B2 JP 5287281B2
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- Prior art keywords
- layer
- tire
- pneumatic tire
- layers
- thermoplastic resin
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Description
本発明は、空気入りタイヤの製造方法及び空気入りタイヤに関し、更に詳しくは、熱可塑性樹脂または熱可塑性エラストマー組成物からなるタイヤ構成部材の剥離故障を改善するようにした空気入りタイヤの製造方法及び空気入りタイヤに関する。 The present invention relates to a method for manufacturing a pneumatic tire and a pneumatic tire. More specifically, the present invention relates to a method for manufacturing a pneumatic tire and a method for manufacturing a pneumatic tire to improve a peeling failure of a tire constituent member made of a thermoplastic resin or a thermoplastic elastomer composition. Related to pneumatic tires.
従来、ゴムに代えて、熱可塑性樹脂または熱可塑性樹脂成分とエラストマー成分とをブレンドした熱可塑性エラストマー組成物をインナーライナー層に用いた空気入りタイヤが周知である(例えば、特許文献1参照)。これによりインナーライナー層を軽量化し、燃費を向上することができる利点がある。 Conventionally, pneumatic tires using a thermoplastic elastomer or a thermoplastic elastomer composition obtained by blending a thermoplastic resin component and an elastomer component instead of rubber as an inner liner layer are well known (see, for example, Patent Document 1). Thereby, there is an advantage that the inner liner layer can be reduced in weight and fuel efficiency can be improved.
しかしながら、熱可塑性樹脂または熱可塑性エラストマー組成物からインナーライナー層を構成すると、従来のゴムに比べて剛直であるため、カーカスバンドを膨径させてグリーンタイヤを成形する際に、そのリフト変形率(膨径率)が高いと、弾性戻り現象によりインナーライナー層が剥離する剥離現象が生じ、タイヤ故障になることがある。特にリフト変形率が160%を超えるような高扁平タイヤ、重荷重用タイヤ、航空機用タイヤ、建設車両用タイヤなどで剥離故障が発生し易い。 However, when the inner liner layer is composed of a thermoplastic resin or a thermoplastic elastomer composition, the inner liner layer is more rigid than the conventional rubber. Therefore, when the green tire is formed by expanding the carcass band, the lift deformation rate ( When the expansion ratio is high, a peeling phenomenon in which the inner liner layer peels due to an elastic return phenomenon may occur, resulting in a tire failure. In particular, a peeling failure is likely to occur in a high flat tire having a lift deformation rate exceeding 160%, a heavy load tire, an aircraft tire, a construction vehicle tire, and the like.
本発明の目的は、熱可塑性樹脂または熱可塑性エラストマー組成物からなるタイヤ構成部材の剥離故障を改善することが可能な空気入りタイヤの製造方法及び空気入りタイヤを提供することにある。 The objective of this invention is providing the manufacturing method of a pneumatic tire and a pneumatic tire which can improve the peeling failure of the tire structural member which consists of a thermoplastic resin or a thermoplastic elastomer composition.
上記目的を達成する本発明の空気入りタイヤの製造方法は、成形ドラム上で成形した、熱可塑性樹脂または熱可塑性樹脂成分とエラストマー成分とをブレンドした熱可塑性エラストマー組成物からなる環状のタイヤ構成部材を有するカーカスバンドを膨径させてグリーンタイヤを成形するにあたって、前記タイヤ構成部材を積層した複数の層から構成し、内側の層を取り付けた後、成形ドラムを所定量拡径して外側の層を該内側の層上に取り付ける空気入りタイヤの製造方法であって、
前記タイヤ構成部材がインナーライナー層であり、前記複数の層は外側に位置する層程厚さが厚く及び/または弾性率が高いことを特徴とする。
The method for producing a pneumatic tire according to the present invention that achieves the above object comprises an annular tire constituent member formed of a thermoplastic resin or a thermoplastic elastomer composition blended with a thermoplastic resin component and an elastomer component molded on a molding drum. when the carcass band is radially expanded to form a green tire having, composed of a plurality of layers formed by stacking the tire components, after attaching the inner layer, outer layer of the forming drum by a predetermined amount expanded A method of manufacturing a pneumatic tire for mounting on the inner layer ,
The tire constituent member is an inner liner layer, and the plurality of layers are thicker and / or have a higher elastic modulus as the outer layer is located .
本発明の空気入りタイヤは、熱可塑性樹脂または熱可塑性樹脂成分とエラストマー成分とをブレンドした熱可塑性エラストマー組成物からなるインナーライナー層を有する空気入りタイヤにおいて、前記インナーライナー層をタイヤ内側から外側に積層した複数の層から構成し、該複数の層はタイヤ外側に位置する層程厚さが厚く及び/または弾性率が高いことを特徴とする。 The pneumatic tire of the present invention is a pneumatic tire having an inner liner layer made of a thermoplastic elastomer composition in which a thermoplastic resin or a thermoplastic resin component and an elastomer component are blended, and the inner liner layer is arranged from the inside to the outside of the tire. The plurality of layers are composed of a plurality of layers, and the plurality of layers are characterized in that the layer located on the outer side of the tire is thicker and / or has a higher elastic modulus.
上述した本発明によれば、熱可塑性樹脂または熱可塑性エラストマー組成物からなるタイヤ構成部材を複数の層から構成することにより、各層の剛直度合いが低下し、そのように剛直度合いを下げた層において、内側の層を取り付けた後、成形ドラムを所定量拡径して外側の層を取り付けることにより、弾性戻り現象による剥離に大きく影響する外側の層の膨径量をカーカスバンド膨径時に下げることができるので、剥離故障の改善が可能になる。 According to the present invention described above, by constituting a tire constituent member made of a thermoplastic resin or a thermoplastic elastomer composition from a plurality of layers, the degree of rigidity of each layer is reduced, and in such a layer where the degree of rigidity is lowered. After attaching the inner layer, the molding drum is expanded by a predetermined amount and the outer layer is attached, so that the expansion amount of the outer layer, which greatly affects the peeling due to the elastic return phenomenon, is lowered when the carcass band expands. Therefore, it is possible to improve the peeling failure.
以下、本発明の実施の形態について添付の図面を参照しながら詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
図1は、本発明の空気入りタイヤの一実施形態を示し、1はトレッド部、2はサイドウォール部、3はビード部である。 FIG. 1 shows an embodiment of the pneumatic tire of the present invention, where 1 is a tread portion, 2 is a sidewall portion, and 3 is a bead portion.
左右のビード部3間にタイヤ径方向に延在する補強コードをタイヤ周方向に所定の間隔で配置してゴム層に埋設したカーカス層4が延設され、その両端部がビード部3に埋設したビードコア5の周りにビードフィラー6を挟み込むようにしてタイヤ軸方向内側から外側に折り返されている。
A
トレッド部1のカーカス層4の外周側には、複数のベルト層7が設けられている。ベルト層7の外周側にはトレッドゴム層8が配設されている。カーカス層4の内側にはタイゴム層9を介して、熱可塑性樹脂または熱可塑性樹脂成分とエラストマー成分とをブレンドした熱可塑性エラストマー組成物からなるフィルム状のインナーライナー層10が配置されている。
A plurality of
インナーライナー層10は、図2に示すように、弾性率が同じ複数の層10A,10B,10Cから構成されている。タイヤ内側から外側に積層される複数の層10A,10B,10Cは、最も内側に位置する最内層10Aと、その外側に位置する第2層10Bと、その外側に位置する第3層10Cからなり、タイヤ外側に位置する層程厚さが厚くなっている。インナーライナー層10の複数の層は、図示する例では3層を示すが、2層であっても4層以上であってもよく、タイヤのサイズや種類により適宜選択することができる。
As shown in FIG. 2, the
サイドウォール部2のカーカス層4の外側にはサイドゴム層11が配設されている。ビード部3のカーカス層4の折り返し部外側にはリムクッションゴム層12が設けられている。
A
以下、図3〜7を参照しながら、本発明の製造方法により図1の空気入りタイヤを製造する方法を説明する。 Hereinafter, a method of manufacturing the pneumatic tire of FIG. 1 by the manufacturing method of the present invention will be described with reference to FIGS.
先ず、図3に示すように、成形ドラム21上に熱可塑性樹脂または熱可塑性エラストマー組成物からなる筒状のインナーライナー層最内層10Aを取り付ける。続いて、図4に示すように成形ドラム21を所定量拡径させる。拡径量としては、第2層10Bの厚さにより適宜選択することができ、例えば、110%(最内層10Aを取り付けた状態の成形ドラム21の径に対して)にすることができる。拡径後、最内層10Aの外周側に最内層10Aより厚い帯状の第2層10Bを環状に巻き付け、第2層10Bを最内層10A上に貼り合せる。
First, as shown in FIG. 3, a cylindrical inner liner layer
次いで、図5に示すように、成形ドラム21を更に所定量拡径させる。拡径量としては、第3層10Cの厚さにより適宜選択することができ、例えば、120%(最内層10Aを取り付けた状態の成形ドラム21の径に対して)にすることができる。拡径後、第2層10Bの外周側に第2層10Bより厚い帯状の第3層10Cを環状に巻き付け、第3層10Cを第2層10B上に貼り合せる。これにより、成形ドラム21上に熱可塑性樹脂または熱可塑性エラストマー組成物からなる筒状のインナーライナー層10が成形される。
Next, as shown in FIG. 5, the diameter of the forming
第3層10C上に接着剤を塗布した後、従来と同様にして、未加硫のタイゴム層9、未加硫のカーカス層4、未加硫のビードフィラー6を取り付けたビードコア5、未加硫のリムクッションゴム層12、未加硫のサイドゴム層11を順次取り付けて、筒状のカーカスバンド13を成形する(図6参照)。
After applying the adhesive on the
カーカスバンド13を成形ドラム21から外し、図7に示すようにシェーピングドラム22に取り付けて内圧を付与し、それによりカーカスバンド13をトロイダル状に膨張させて、カーカスバンド13の外周側に配置した、未加硫のベルト層7の外周側に未加硫のトレッドゴム層8を貼り合わせた環状のベルトバンド14の内周側に圧着し、グリーンタイヤを成形する。このグリーンタイヤをモールド内で加圧加熱して加硫し、図1の空気入りタイヤを得る。
The
上述した本発明では、インナーライナー層10を複数の層10A,10B,10Cから構成することにより、各層の剛直度合いが低下し、そのように剛直度合いを下げた層10A,10B,10Cにおいて、内側の層10A(10B)を取り付けた後、成形ドラム21を所定量拡径して外側の層10B(10C)を取り付けることにより、弾性戻り現象によるタイゴム層9との剥離に大きく影響する外側の層の膨径量をカーカスバンド膨径時に下げることができるので、インナーライナー層10がタイゴム層9から剥離する剥離故障を改善することができる。
In the present invention described above, the
また、内側の層10A(10B)を取り付けた後、成形ドラム21を所定量拡径して外側の層10B(10C)を取り付けることにより、弾性戻り現象を抑制しながら、外側の層の厚さを順次厚くすることができるので、所望の特性(耐空気透過防止性)に必要な厚さのインナーライナー層10を成形ドラム21の拡径回数を最小回数で成形することができる利点がある。
Further, after the
本発明において、最内層10Aの厚さとしては、150μm以下にするのがよい。最内層10Aの厚さが150μmを超えると、カーカスバンド13の膨径率が最内層10Aにおいて160%以上あるような大きいリフト変形が最内層10Aに加わった際に追従し難くなる。好ましくは、100μm以下がよい。下限値は生産性の点から40μm以上がよい。
In the present invention, the thickness of the
成形ドラム21の拡径率としては、最も外側に位置する第3層10Cを取り付ける時の成形ドラム21の拡径率が最内層10Aを取り付けた状態での成形ドラム21の径に対して130%以下になるようにするのがよい。この拡径率が130%を超えると、ビードコア5を取り付ける際に縮径させるインナーライナー層10の端部に発生するシワによりエア溜りが生じる原因となる。好ましくは、120%以下がよい。
The diameter expansion rate of the
インナーライナー層10の複数の層10A,10B,10Cは、弾性率が同じ材料から構成したが、弾性率が異なる材料から構成するようにしてもよい。その場合、外側に位置する層程弾性率を高くするのが上記と同じ理由からよい。弾性率が異なる各層の厚さは同じである。或いは、両者を組み合わせるようにしてもよく、外側に位置する層程厚さが厚くかつ弾性率が高くなるようにしてもよい。
The plurality of
インナーライナー層10の各層に使用する熱可塑性樹脂と熱可塑性エラストマー組成物の弾性率(貯蔵弾性率)としては1〜500MPaの範囲にするのがよい。弾性率が1MPa未満であると、グリーンタイヤ成形時にシワなどが発生して成形加工性が低下し、逆に500MPaを超えると耐久性に問題が生じる。好ましくは、25〜400MPaがよい。なお、ここで言う貯蔵弾性率は、東洋精機製作所製の粘弾性スペクロトメータを用い、静歪み10%、動歪み±2%、周波数20Hz、温度20℃の条件下で測定する貯蔵弾性率である。
The elastic modulus (storage elastic modulus) of the thermoplastic resin and the thermoplastic elastomer composition used for each layer of the
インナーライナー層10の各層に使用する熱可塑性樹脂と熱可塑性エラストマー組成物の空気透過係数としては、25×10-12 cc・cm/cm2 ・sec ・cmHg以下とするのが好ましい。空気透過係数が25×10-12 cc・cm/cm2 ・sec ・cmHgを超えると、内圧を保持するために厚さを厚くしなければならず、タイヤの軽量化の点から好ましくない。
The air permeability coefficient of the thermoplastic resin and the thermoplastic elastomer composition used for each layer of the
本発明では、インナーライナー層10に用いられる熱可塑性樹脂としては、例えば、ポリアミド系樹脂〔例えば、ナイロン6(N6)、ナイロン66(N66)、ナイロン46(N46)、ナイロン11(N11)、ナイロン12(N12)、ナイロン610(N610)、ナイロン612(N612)、ナイロン6/66共重合体(N6/66)、ナイロン6/66/610共重合体(N6/66/610)、ナイロンMXD6(MXD6)、ナイロン6T、ナイロン6/6T共重合体、ナイロン66/PP共重合体、ナイロン66/PPS共重合体〕及びそれらのN−アルコキシアルキル化物〔例えば、ナイロン6のメトキシメチル化物、ナイロン6/610共重合体のメトキシメチル化物、ナイロン612のメトキシメチル化物〕、ポリエステル系樹脂〔例えば、ポリブチレンテレフタレート(PBT)、ポリエチレンテレフタレート(PET)、ポリエチレンイソフタレート(PEI)、PET/PEI共重合体、ポリアリレート(PAR)、ポリブチレンナフタレート(PBN)、液晶ポリエステル、ポリオキシアルキレンジイミドジ酸/ポリブチレンテレフタレート共重合体などの芳香族ポリエステル〕、ポリニトリル系樹脂〔例えば、ポリアクリロニトリル(PAN)、ポリメタクリロニトリル、アクリロニトリル/スチレン共重合体(AS)、(メタ)アクリロニトリル/スチレン共重合体、(メタ)アクリロニトリル/スチレン/ブタジエン共重合体〕、ポリメタクリレート系樹脂〔例えば、ポリメタクリル酸メチル(PMMA)、ポリメタクリル酸エチル〕、ポリビニル系樹脂〔例えば、酢酸ビニル、ポリビニルアルコール(PVA)、ビニルアルコール/エチレン共重合体(EVOH)、ポリ塩化ビニリデン(PDVC)、ポリ塩化ビニル(PVC)、塩化ビニル/塩化ビニリデン共重合体、塩化ビニリデン/メチルアクリレート共重合体、塩化ビニリデン/アクリロニトリル共重合体(ETFE)〕、セルロース系樹脂〔例えば、酢酸セルロース、酢酸酪酸セルロース〕、フッ素系樹脂〔例えば、ポリフッ化ビニリデン(PVDF)、ポリフッ化ビニル(PVF)、ポリクロルフルオロエチレン(PCTFE)、テトラフロロエチレン/エチレン共重合体〕、イミド系樹脂〔例えば、芳香族ポリイミド(PI)〕等を好ましく用いることができる。 In the present invention, examples of the thermoplastic resin used for the inner liner layer 10 include polyamide resins [eg, nylon 6 (N6), nylon 66 (N66), nylon 46 (N46), nylon 11 (N11), nylon 12 (N12), nylon 610 (N610), nylon 612 (N612), nylon 6/66 copolymer (N6 / 66), nylon 6/66/610 copolymer (N6 / 66/610), nylon MXD6 ( MXD6), nylon 6T, nylon 6 / 6T copolymer, nylon 66 / PP copolymer, nylon 66 / PPS copolymer] and their N-alkoxyalkylated products ( for example, methoxymethylated products of nylon 6, nylon 6) / 610 Methoxymethylated Copolymer, Nylon612 Methoxymethylated ] Reester resin [for example, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), PET / PEI copolymer, polyarylate (PAR), polybutylene naphthalate (PBN), liquid crystal polyester, Aromatic polyester such as polyoxyalkylene diimide diacid / polybutylene terephthalate copolymer], polynitrile resin [for example, polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), (meth) Acrylonitrile / styrene copolymer, (meth) acrylonitrile / styrene / butadiene copolymer], polymethacrylate resin [for example, polymethyl methacrylate (PMMA), polyethyl methacrylate], Livinyl resin [eg, vinyl acetate, polyvinyl alcohol (PVA), vinyl alcohol / ethylene copolymer (EVOH), polyvinylidene chloride (PDVC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymer, chloride Vinylidene / methyl acrylate copolymer, vinylidene chloride / acrylonitrile copolymer (ETFE)], cellulose resin [eg, cellulose acetate, cellulose acetate butyrate], fluorine resin [eg, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polychlorofluoroethylene (PCTFE), tetrafluoroethylene / ethylene copolymer], an imide resin [for example, aromatic polyimide (PI)] and the like can be preferably used.
熱可塑性エラストマー組成物は、上述した熱可塑性樹脂の成分にエラストマー成分を混合して構成することができる。使用されるエラストマーとしては、例えば、ジエン系ゴム及びその水添物〔例えば、天然ゴム(NR)、イソプレンゴム(IR)、エポキシ化天然ゴム、スチレンブタジエンゴム(SBR)、ブタジエンゴム(BR、高シスBR及び低シスBR)、ニトリルゴム(NBR)、水素化NBR、水素化SBR〕、オレフィン系ゴム〔例えば、エチレンプロピレンゴム(EPDM、EPM)、マレイン酸変性エチレンプロピレンゴム(M−EPM)、ブチルゴム(IIR)、イソブチレンと芳香族ビニル又はジエン系モノマー共重合体、アクリルゴム(ACM)、アイオノマー〕、含ハロゲンゴム〔例えば、Br−IIR、CI−IIR、イソブチレンパラメチルスチレン共重合体の臭素化物(Br−IPMS)、クロロプレンゴム(CR)、ヒドリンゴム(CHR)、クロロスルホン化ポリエチレンゴム(CSM)、塩素化ポリエチレンゴム(CM)、マレイン酸変性塩素化ポリエチレンゴム(M−CM)〕、シリコンゴム〔例えば、メチルビニルシリコンゴム、ジメチルシリコンゴム、メチルフェニルビニルシリコンゴム〕、含イオウゴム〔例えば、ポリスルフィドゴム〕、フッ素ゴム〔例えば、ビニリデンフルオライド系ゴム、含フッ素ビニルエーテル系ゴム、テトラフルオロエチレン−プロピレン系ゴム、含フッ素シリコン系ゴム、含フッ素ホスファゼン系ゴム〕、熱可塑性エラストマー〔例えば、スチレン系エラストマー、オレフィン系エラストマー、エステル系エラストマー、ウレタン系エラストマー、ボリアミド系エラストマー)等を好ましく使用することができる。 The thermoplastic elastomer composition can be constituted by mixing an elastomer component with the above-described thermoplastic resin component. Examples of the elastomer used include diene rubber and hydrogenated products thereof [for example, natural rubber (NR), isoprene rubber (IR), epoxidized natural rubber, styrene butadiene rubber (SBR), butadiene rubber (BR, high Cis BR and low cis BR), nitrile rubber (NBR), hydrogenated NBR, hydrogenated SBR], olefin rubber [for example, ethylene propylene rubber (EPDM, EPM), maleic acid modified ethylene propylene rubber (M-EPM), Butyl rubber (IIR), isobutylene and aromatic vinyl or diene monomer copolymer, acrylic rubber (ACM), ionomer], halogen-containing rubber [for example, Br-IIR, CI-IIR, bromine of isobutylene paramethylstyrene copolymer (Br-IPMS), chloroprene rubber (CR), hydride Rubber (CHR), chlorosulfonated polyethylene rubber (CSM), chlorinated polyethylene rubber (CM), maleic acid-modified chlorinated polyethylene rubber (M-CM)], silicone rubber [eg, methyl vinyl silicone rubber, dimethyl silicone rubber, Methyl phenyl vinyl silicon rubber], sulfur-containing rubber (for example, polysulfide rubber), fluorine rubber (for example, vinylidene fluoride rubber, fluorine-containing vinyl ether rubber, tetrafluoroethylene-propylene rubber, fluorine-containing silicon rubber, fluorine-containing phosphazene) Rubbers], thermoplastic elastomers (for example, styrene elastomers, olefin elastomers, ester elastomers, urethane elastomers, polyamide elastomers) and the like can be preferably used.
上記した特定の熱可塑性樹脂成分とエラストマー成分との相溶性が異なる場合は、第3成分として適当な相溶化剤を用いて両者を相溶化させることができる。ブレンド系に相溶化剤を混合することにより、熱可塑性樹脂とエラストマー成分との界面張力が低下し、その結果、分散相を形成しているゴム粒子径が微細になることから両成分の特性はより有効に発現されることになる。そのような相溶化剤としては、一般的に熱可塑性樹脂及びエラストマー成分の両方又は片方の構造を有する共重合体、或いは熱可塑性樹脂又はエラストマー成分と反応可能なエポキシ基、カルボニル基、ハロゲン基、アミノ基、オキサゾリン基、水酸基等を有した共重合体の構造をとるものとすることができる。これらは混合される熱可塑性樹脂とエラストマー成分の種類によって選定すればよいが、通常使用されるものには、スチレン/エチレン・ブチレンブロック共重合体(SEBS)及びそのマレイン酸変性物、EPDM、EPM、EPDM/スチレン又はEPDM/アクリロニトリルグラフト共重合体及びそのマレイン酸変性物、スチレン/マレイン酸共重合体、反応性フェノキシン等を挙げることができる。かかる相溶化剤の配合量には特に限定はないが、好ましくは、ポリマー成分(熱可塑性樹脂とエラストマー成分との合計)100重量部に対して、0.5〜10重量部がよい。 When the above-mentioned specific thermoplastic resin component and the elastomer component are different in compatibility, they can be made compatible by using a suitable compatibilizer as the third component. By mixing the compatibilizer with the blend system, the interfacial tension between the thermoplastic resin and the elastomer component decreases, and as a result, the diameter of the rubber particles forming the dispersed phase becomes fine. It will be expressed more effectively. As such a compatibilizing agent, generally a copolymer having a structure of both or one of the thermoplastic resin and the elastomer component, or an epoxy group, a carbonyl group, a halogen group, which can react with the thermoplastic resin or the elastomer component, The structure of a copolymer having an amino group, an oxazoline group, a hydroxyl group and the like can be taken. These may be selected according to the kind of the thermoplastic resin and the elastomer component to be mixed, but those usually used include styrene / ethylene butylene block copolymer (SEBS) and its maleic acid modified product, EPDM, EPM. EPDM / styrene or EPDM / acrylonitrile graft copolymer and its maleic acid modified product, styrene / maleic acid copolymer, reactive phenoxin and the like. The amount of the compatibilizing agent is not particularly limited, but is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the polymer component (the total of the thermoplastic resin and the elastomer component).
熱可塑性樹脂とエラストマーとをブレンドする場合の特定の熱可塑性樹脂成分(A)とエラストマー成分(B)との組成比は、特に限定はなく、フィルムの厚さ、耐空気透過性、柔軟性のバランスで適宜決めればよいが、好ましい範囲は重量比(A)/(B)で10/90〜90/10、更に好ましくは15/85〜90/10である。 The composition ratio of the specific thermoplastic resin component (A) and the elastomer component (B) in the case of blending the thermoplastic resin and the elastomer is not particularly limited, and the film thickness, air permeation resistance, flexibility The weight range (A) / (B) is preferably 10/90 to 90/10, more preferably 15/85 to 90/10.
本発明に係る熱可塑性エラストマー組成物には、上記必須ポリマー成分に加えて、本発明のタイヤ用熱可塑性エラストマー組成物の必要特性を損なわない範囲で前記した相溶化剤ポリマーなどの他のポリマーを混合することができる。他のポリマーを混合する目的は、熱可塑性樹脂とエラストマー成分との相溶性を改良するため、材料の成型加工性をよくするため、耐熱性向上のため、コストダウンのため等があり、これに用いられる材料としては、例えば、ポリエチレン(PE)ポリプロピレン(PP)、ポリスチレン(PS)、ABS、SBS、ポリカーボネート(PC)等を例示することができる。本発明に係るポリマー組成物には、更に一般的にポリマー配合物に配合される充填剤(炭酸カルシウム、酸化チタン、アルミナ等)、カーボンブラック、ホワイトカーボン等の補強剤、軟化剤、可塑剤、加工助剤、顔料、染料、老化防止剤等を上記弾性率の要件を損なわない限り任意に配合することもできる。 In addition to the essential polymer component, the thermoplastic elastomer composition according to the present invention includes other polymers such as the above-described compatibilizer polymer as long as the necessary characteristics of the thermoplastic elastomer composition for tires of the present invention are not impaired. Can be mixed. The purpose of mixing other polymers is to improve the compatibility between the thermoplastic resin and the elastomer component, to improve the molding processability of the material, to improve heat resistance, to reduce costs, etc. Examples of the material used include polyethylene (PE) polypropylene (PP), polystyrene (PS), ABS, SBS, polycarbonate (PC) and the like. In the polymer composition according to the present invention, fillers (calcium carbonate, titanium oxide, alumina, etc.), carbon black, white carbon and other reinforcing agents generally blended in polymer blends, softeners, plasticizers, Processing aids, pigments, dyes, anti-aging agents, and the like can be arbitrarily added as long as the above elastic modulus requirements are not impaired.
また、上記エラストマー成分は熱可塑性樹脂との混合の際、動的に加硫することもできる。動的に加硫する場合の加硫剤、加硫助剤、加硫条件(温度、時間)等は、添加するエラストマー成分の組成に応じて適宜決定すればよく、特に限定されるものではない。 The elastomer component can also be dynamically vulcanized when mixed with a thermoplastic resin. The vulcanizing agent, vulcanization aid, vulcanization conditions (temperature, time), etc. when dynamically vulcanizing may be appropriately determined according to the composition of the elastomer component to be added, and are not particularly limited. .
加硫剤としては、一般的なゴム加硫剤(架橋剤)を用いることができる。具体的には、イオン系加硫剤としては粉末イオウ、沈降性イオウ、高分散性イオウ、表面処理イオウ、不溶性イオウ、ジモルフォリンジサルファイド、アルキルフェノールジサルファイド等を例示でき、例えば、0.5〜4phr〔phr:ゴム成分(エラストマー)100重量部あたりの重量部〕程度用いることができる。 A general rubber vulcanizing agent (crosslinking agent) can be used as the vulcanizing agent. Specific examples of the ionic vulcanizing agent include powdered sulfur, precipitated sulfur, highly dispersible sulfur, surface-treated sulfur, insoluble sulfur, dimorpholine disulfide, alkylphenol disulfide, and the like. About 4 phr [phr: parts by weight per 100 parts by weight of rubber component (elastomer)] can be used.
また、有機過酸化物系の加硫剤としては、ベンゾイルパーオキサイド、t−ブチルヒドロパーオキサイド、2,4−ジクロロベンゾイルパーオキサイド、2,5−ジメチル−2,5−ジ(t−ブチルパーオキシ)ヘキサン、2,5−ジメチルヘキサン−2,5−ジ(パーオキシルベンゾエート)等が例示され、例えば、1〜20phr 程度用いることができる。 Organic peroxide vulcanizing agents include benzoyl peroxide, t-butyl hydroperoxide, 2,4-dichlorobenzoyl peroxide, 2,5-dimethyl-2,5-di (t-butyl peroxide). Oxy) hexane, 2,5-dimethylhexane-2,5-di (peroxylbenzoate), etc. are exemplified, and for example, about 1 to 20 phr can be used.
更に、フェノール樹脂系の加硫剤としては、アルキルフェノール樹脂の臭素化物や、塩化スズ、クロロプレン等のハロゲンドナーとアルキルフェノール樹脂とを含有する混合架橋系等が例示でき、例えば、1〜20phr 程度用いることができる。その他として、亜鉛華(5phr 程度)、酸化マグネシウム(4phr 程度) 、リサージ(10〜20phr 程度) 、p−キノンジオキシム、p−ジベンゾイルキノンジオキシム、テトラクロロ−p−ベンゾキノン、ポリ−p−ジニトロソベンゼン(2〜10phr 程度) 、メチレンジアニリン(0.2〜10phr 程度) が例示できる。 Furthermore, examples of the phenol resin-based vulcanizing agent include bromides of alkyl phenol resins, mixed crosslinking systems containing halogen donors such as tin chloride and chloroprene, and alkyl phenol resins. For example, about 1 to 20 phr is used. Can do. In addition, zinc white (about 5 phr), magnesium oxide (about 4 phr), risurge (about 10-20 phr), p-quinonedioxime, p-dibenzoylquinonedioxime, tetrachloro-p-benzoquinone, poly-p- Examples thereof include dinitrosobenzene (about 2 to 10 phr) and methylenedianiline (about 0.2 to 10 phr).
また、必要に応じて、加硫促進剤を添加してもよい。加硫促進剤としては、アルデヒド・アンモニア系、グアニジン系、チアゾール系、スルフェンアミド系、チウラム系、ジチオ酸塩系、チオウレア系等の一般的な加硫促進剤を、例えば、0.5〜2phr 程度用いることができる。具体的には、アルデヒド・アンモニア系加硫促進剤としては、ヘキサメチレンテトラミン等、グアジニン系加硫促進剤としては、ジフェニルグアジニン等、チアゾール系加硫促進剤としては、ジベンゾチアジルジサルファイド(DM)、2−メルカプトベンゾチアゾール及びそのZn塩、シクロヘキシルアミン塩等、スルフェンアミド系加硫促進剤としては、シクロヘキシルベンゾチアジルスルフェンアマイド(CBS)、N−オキシジエチレンベンゾチアジル−2−スルフェンアマイド、N−t−ブチル−2−ベンゾチアゾールスルフェンアマイド、2−(チモルポリニルジチオ)ベンゾチアゾール等、チウラム系加硫促進剤としては、テトラメチルチウラムジサルファイド(TMTD)、テトラエチルチウラムジサルファイド、テトラメチルチウラムモノサルファイド(TMTM)、ジペンタメチレンチウラムテトラサルファイド等、ジチオ酸塩系加硫促進剤としては、Zn−ジメチルジチオカーバメート、Zn−ジエチルジチオカーバメート、Zn−ジ−n−ブチルジチオカーバメート、Zn−エチルフェニルジチオカーバメート、Te−ジエチルジチオカーバメート、Cu−ジメチルジチオカーバメート、Fe−ジメチルジチオカーバメート、ピペコリンピペコリルジチオカーバメート等、チオウレア系加硫促進剤としては、エチレンチオウレア、ジエチルチオウレア等を挙げることができる。 Moreover, you may add a vulcanization accelerator as needed. Examples of the vulcanization accelerator include general vulcanization accelerators such as aldehyde / ammonia, guanidine, thiazole, sulfenamide, thiuram, dithioate, thiourea, etc. About 2 phr can be used. Specifically, as the aldehyde / ammonia vulcanization accelerator, hexamethylenetetramine and the like, as the guanidinium vulcanization accelerator, diphenyl guanidine, etc., as the thiazole vulcanization accelerator, dibenzothiazyl disulfide ( DM), 2-mercaptobenzothiazole and its Zn salt, cyclohexylamine salt and the like, sulfenamide vulcanization accelerators include cyclohexylbenzothiazylsulfenamide (CBS), N-oxydiethylenebenzothiazyl-2- As thiuram vulcanization accelerators such as sulfenamide, Nt-butyl-2-benzothiazole sulfenamide, 2- (thymolpolynyldithio) benzothiazole, tetramethylthiuram disulfide (TMTD), tetraethyl Thiuram disulfide, tetrame Examples of dithioate-based vulcanization accelerators such as lutiuram monosulfide (TMTM) and dipentamethylene thiuram tetrasulfide include Zn-dimethyldithiocarbamate, Zn-diethyldithiocarbamate, Zn-di-n-butyldithiocarbamate, Zn -Ethylphenyldithiocarbamate, Te-diethyldithiocarbamate, Cu-dimethyldithiocarbamate, Fe-dimethyldithiocarbamate, pipecoline pipecolyldithiocarbamate, etc. Examples of thiourea vulcanization accelerators include ethylenethiourea, diethylthiourea, etc. be able to.
また、加硫促進助剤としては、一般的なゴム用助剤を併せて用いることができ、例えば、亜鉛華(5phr 程度)、ステアリン酸やオレイン酸及びこれらのZn塩(2〜4phr 程度)等が使用できる。熱可塑性エラストマー組成物の製造方法は、予め熱可塑性樹脂成分とエラストマー成分(ゴムの場合は未加硫物)とを2軸混練押出機等で溶融混練し、連続相(マトリックス)を形成する熱可塑性樹脂中に分散相(ドメイン)としてエラストマー成分を分散させることによる。エラストマー成分を加硫する場合には、混練下で加硫剤を添加し、エラストマー成分を動的加硫させてもよい。また、熱可塑性樹脂またはエラストマー成分への各種配合剤(加硫剤を除く)は、上記混練中に添加してもよいが、混練の前に予め混合しておくことが好ましい。熱可塑性樹脂とエラストマー成分の混練に使用する混練機としては、特に限定はなく、スクリュー押出機、ニーダ、バンバリミキサー、2軸混練押出機等が使用できる。中でも熱可塑性樹脂とエラストマー成分の混練およびエラストマー成分の動的加硫には、2軸混練押出機を使用するのが好ましい。更に、2種類以上の混練機を使用し、順次混練してもよい。溶融混練の条件として、温度は熱可塑性樹脂が溶融する温度以上であればよい。また、混練時の剪断速度は1000〜7500Sec -1であるのが好ましい。混練全体の時間は30秒から10分、また加硫剤を添加した場合には、添加後の加硫時間は15秒から5分であるのが好ましい。上記方法で作製された熱可塑性エラストマー組成物は、射出成形、押出し成形等、通常の熱可塑性樹脂の成形方法によって所望のフィルム形状にすればよい。 Moreover, as a vulcanization | cure acceleration | stimulation adjuvant, the general rubber adjuvant can be used together, for example, zinc white (about 5 phr), stearic acid, oleic acid, and these Zn salts (about 2-4 phr) Etc. can be used. A method for producing a thermoplastic elastomer composition is a method in which a thermoplastic resin component and an elastomer component (unvulcanized product in the case of rubber) are previously melt-kneaded with a twin-screw kneading extruder or the like to form a continuous phase (matrix). By dispersing the elastomer component as a dispersed phase (domain) in the plastic resin. When vulcanizing the elastomer component, a vulcanizing agent may be added under kneading to dynamically vulcanize the elastomer component. Further, various compounding agents (excluding the vulcanizing agent) to the thermoplastic resin or the elastomer component may be added during the kneading, but are preferably mixed in advance before kneading. The kneading machine used for kneading the thermoplastic resin and the elastomer component is not particularly limited, and a screw extruder, a kneader, a Banbury mixer, a biaxial kneading extruder, or the like can be used. Among them, it is preferable to use a twin-screw kneading extruder for kneading the thermoplastic resin and the elastomer component and for dynamic vulcanization of the elastomer component. Further, two or more types of kneaders may be used and kneaded sequentially. As conditions for melt kneading, the temperature may be higher than the temperature at which the thermoplastic resin melts. Moreover, it is preferable that the shear rate at the time of kneading | mixing is 1000-7500Sec < -1 >. The entire kneading time is from 30 seconds to 10 minutes, and when a vulcanizing agent is added, the vulcanization time after addition is preferably from 15 seconds to 5 minutes. What is necessary is just to make the thermoplastic elastomer composition produced by the said method into a desired film shape with the shaping | molding methods of normal thermoplastic resins, such as injection molding and extrusion molding.
このようにして得られる熱可塑性エラストマー組成物は、熱可塑性樹脂(A)のマトリクス中にエラストマー成分(B)が不連続相として分散した構造をとる。かかる構造をとることにより、フィルムに十分な柔軟性と連続相としての樹脂層の効果により十分な剛性を併せ付与することができると共に、エラストマー成分の多少によらず、成形に際し、熱可塑性樹脂と同等の成形加工性を得ることができる。 The thermoplastic elastomer composition thus obtained has a structure in which the elastomer component (B) is dispersed as a discontinuous phase in the matrix of the thermoplastic resin (A). By adopting such a structure, the film can be provided with sufficient flexibility and sufficient rigidity due to the effect of the resin layer as a continuous phase, and at the time of molding, regardless of the amount of the elastomer component, Equivalent moldability can be obtained.
隣接するタイヤ構成部材との接着は、通常のゴム系、フェノール樹脂系、アクリル共重合体系、イソシアネート系等のポリマーと架橋剤を溶剤に溶かした接着剤を塗布し、加硫成形時の熱と圧力により接着させる方法、または、スチレンブタジエンスチレン共重合体(SBS)、エチレンエチルアクリレート(EEA)、スチレンエチレンブチレンブロック共重合体(SEBS)等の接着用樹脂をフィルムと共に共押出、或いはラミネートして多層積層体を作製しておき、加硫時に隣接するタイヤ構成部材と接着させる方法がある。溶剤系接着剤としては、例えば、フェノール樹脂系(ケムロック220・ロード社)、塩化ゴム系(ケムロック205、ケムロック234B)、イソシアネート系(ケムロック402)等を例示することができる。 Adhesion between adjacent tire components is performed by applying an ordinary rubber-based, phenolic resin-based, acrylic copolymer-based, isocyanate-based polymer and an adhesive in which a crosslinking agent is dissolved in a solvent, and heat generated during vulcanization molding. A method of adhering by pressure, or a co-extrusion or laminating adhesive resin such as styrene butadiene styrene copolymer (SBS), ethylene ethyl acrylate (EEA), styrene ethylene butylene block copolymer (SEBS) or the like. There is a method in which a multilayer laminate is prepared and bonded to an adjacent tire constituent member during vulcanization. Examples of the solvent-based adhesive include phenol resin (Chemlock 220, Rhode), chlorinated rubber (Chemlock 205, Chemlock 234B), isocyanate (Chemlock 402), and the like.
本発明は、上述した実施形態に示すように、熱可塑性樹脂または熱可塑性エラストマー組成物からなるインナーライナー層10に適用することができるが、それに限定されず、同様の問題がある熱可塑性樹脂または熱可塑性エラストマー組成物からなるタイヤ構成部材であれば、いずれのタイヤ構成部材にも用いることができる。
The present invention can be applied to the
本発明は、特にリフト変形率が160%を超えるような高扁平タイヤ、重荷重用タイヤ、航空機用タイヤ、建設車両用タイヤなどの空気入りタイヤに好ましく適用することができる。 The present invention can be preferably applied to pneumatic tires such as high flat tires having a lift deformation rate exceeding 160%, heavy load tires, aircraft tires, construction vehicle tires and the like.
タイヤサイズを255/45R18にし、熱可塑性エラストマー組成物(ナイロン6/66共重合体(東レ社製アミランCM6001)とイソブチレンパラメチルスチレン共重合体の臭素化物(エクソンモービルケミカル社製MDX90−10)とのブレンド)からなるインナーライナー層を厚さ100μmの最内層と厚さ150μmの第2層(弾性率は共に100MPa)から構成し、第2層取り付け時の成形ドラムの拡径率を160%にして図1に示す構成(但し、インナーライナー層は2層からなる)を有するグリーンタイヤを成形した(本発明の方法1)。
The tire size is 255 / 45R18, and a thermoplastic elastomer composition (
また、タイヤサイズを上記と同じにし、インナーライナー層を弾性率100MPaの最内層と弾性率200MPaの第2層(厚さは共に100μm)から構成し、第2層取り付け時の成形ドラムの拡径率を160%にして図1に示す構成(但し、インナーライナー層は2層からなる)を有するグリーンタイヤを成形した(本発明の方法2)。最内層及び第2層には、上記と同じ熱可塑性エラストマー組成物を使用し、ナイロン6/66共重合体とイソブチレンパラメチルスチレン共重合体の臭素化物の配合割合を変えることで、弾性率を上記のように調整した。
Also, the tire size is the same as described above, and the inner liner layer is composed of an innermost layer having an elastic modulus of 100 MPa and a second layer having an elastic modulus of 200 MPa (both thicknesses are 100 μm), and the diameter of the forming drum is increased when the second layer is attached. A green tire having the structure shown in FIG. 1 (however, the inner liner layer is composed of two layers) was molded at a rate of 160% (
作製した各グリーンタイヤのインナーライナー層の剥離故障の有無を調べたところ、いずれのグリーンタイヤにもインナーライナー層の剥離故障の発生がなく、剥離故障の改善が確認された。 As a result of examining whether or not there was a peeling failure of the inner liner layer of each of the produced green tires, no peeling failure of the inner liner layer occurred in any of the green tires, and improvement of the peeling failure was confirmed.
10 インナーライナー層(タイヤ構成部材)
10A 最内層
10B 第2層
10C 第3層
21 成形ドラム
23 カーカスバンド
10 Inner liner layer (tire component)
Claims (7)
前記タイヤ構成部材がインナーライナー層であり、前記複数の層は外側に位置する層程厚さが厚いことを特徴とする空気入りタイヤの製造方法。 Were molded on the forming drum, in order to form a green tire is radially expanded carcass band having a thermoplastic resin or a thermoplastic resin component and the elastomer component and comprising a thermoplastic elastomer composition obtained by blending an annular tire component, A method of manufacturing a pneumatic tire comprising a plurality of layers in which the tire constituent members are laminated, attaching an inner layer, and then expanding a molding drum by a predetermined amount and attaching an outer layer on the inner layer. And
The method for producing a pneumatic tire according to claim 1, wherein the tire constituent member is an inner liner layer, and the plurality of layers are thicker toward the outer layer .
前記タイヤ構成部材がインナーライナー層であり、前記複数の層は外側に位置する層程弾性率が高いことを特徴とする空気入りタイヤの製造方法。 In forming a green tire by expanding a carcass band having an annular tire constituent member formed of a thermoplastic elastomer composition in which a thermoplastic resin or a thermoplastic resin component blended with an elastomer component is molded on a molding drum, A method of manufacturing a pneumatic tire comprising a plurality of layers in which the tire constituent members are laminated, attaching an inner layer, and then expanding a molding drum by a predetermined amount and attaching an outer layer on the inner layer. And
The method for producing a pneumatic tire according to claim 1, wherein the tire constituent member is an inner liner layer, and the plurality of layers have higher elastic modulus as the layers are located on the outer side .
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JP2009008779A JP5287281B2 (en) | 2009-01-19 | 2009-01-19 | Pneumatic tire manufacturing method and pneumatic tire |
DE102009057002A DE102009057002B4 (en) | 2009-01-19 | 2009-12-04 | Manufacturing process for a pneumatic tire |
CN201010003546A CN101791872A (en) | 2009-01-19 | 2010-01-15 | Pneumatic tire manufacturing method and pneumatic tire |
US12/689,563 US8357255B2 (en) | 2009-01-19 | 2010-01-19 | Pneumatic tire manufacturing method and pneumatic tire |
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2009
- 2009-01-19 JP JP2009008779A patent/JP5287281B2/en not_active Expired - Fee Related
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JP2010162825A (en) | 2010-07-29 |
US20100181003A1 (en) | 2010-07-22 |
CN101791872A (en) | 2010-08-04 |
US8357255B2 (en) | 2013-01-22 |
DE102009057002A1 (en) | 2010-07-29 |
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